EP0130533A1 - Procédé de préparation d'un ester de l'acide glyoxylique - Google Patents

Procédé de préparation d'un ester de l'acide glyoxylique Download PDF

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Publication number
EP0130533A1
EP0130533A1 EP84107326A EP84107326A EP0130533A1 EP 0130533 A1 EP0130533 A1 EP 0130533A1 EP 84107326 A EP84107326 A EP 84107326A EP 84107326 A EP84107326 A EP 84107326A EP 0130533 A1 EP0130533 A1 EP 0130533A1
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EP
European Patent Office
Prior art keywords
acid ester
entrainer
glyoxylic acid
glyoxylic
reaction mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP84107326A
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German (de)
English (en)
Other versions
EP0130533B1 (fr
Inventor
Robert Kenneth Dr. Driscoll
Ernst Ingo Dr. Leupold
Herbert Dr. Baltes
Wolfgang Dr. Ebertz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
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Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT84107326T priority Critical patent/ATE18759T1/de
Publication of EP0130533A1 publication Critical patent/EP0130533A1/fr
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Publication of EP0130533B1 publication Critical patent/EP0130533B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups

Definitions

  • the present invention relates to a process for producing a glyoxylic acid ester by catalytic oxydehydrogenation of the corresponding glycolic acid ester in the gas phase.
  • glycolic acid esters can be oxydehydrogenated on heterogeneous catalysts in the gas phase to form glyoxylic acid esters.
  • the presence of the water of reaction causes at least partial saponification of the glycolic acid esters and glyoxylic acid esters to give acids and alcohols. This reaction takes place in particular in the condensed phase.
  • the hydrate, the hemiacetal and the acetal of the respective glyoxylic acid ester are formed directly during the condensation of the reaction mixture.
  • the present invention therefore provides a process for the preparation of a glyoxylic acid ester by kata - lytic oxydehydrogenation of the corresponding Glykolklareesters in the gas phase, characterized in that the gaseous reaction mixture formed in the oxydehydrogenation is conducted by dosing of an entraining agent in the central part of a fractionating column, wherein the reaction mixture cools rapidly and the water of reaction and other low boilers are distilled off together with the entraining agent overhead and the glyoxylic acid ester is obtained as the bottom product.
  • glycolic acid esters of the general formula HO-CH 2 -COOR are used in vapor form.
  • R is a hydrocarbon radical, preferably an aliphatic, straight-chain or branched alkyl radical with 1 to 8 C atoms, in particular with 1 to 5 C atoms.
  • the gaseous glycolic acid esters are passed over the catalyst together with oxygen or an oxygen-containing gas such as air. It is preferably diluted with a carrier gas such as nitrogen or noble gases.
  • any oxydehydrogenation catalyst can be used as a catalyst for the process according to the invention.
  • the catalyst preferably contains at least one of the elements V, Au, Mo, Ag, Cu, Sn, Sb, Bi and P.
  • other elements of the 3rd to 5th main group also have a catalytic effect.
  • the elements mentioned are either in metallic form or in the form of their compounds, e.g. introduced into the reaction zone as oxides, nitrates, acetates, acetylacetonates, oxalates, citrates or halides.
  • the catalytically active elements are preferably applied to support materials.
  • Silicates, aluminum oxides, aluminum silicates, pumice or coal are particularly suitable as carriers.
  • Silicates, aluminum oxides or aluminum silicates are preferably used.
  • Aluminum silicates with a BET surface area of less than 50 m 2 / g are particularly advantageous.
  • the total amount of elements on the carrier can vary within wide limits. In general, it is 0.01 to 50 wt .-%, preferably 0.1 to 20 wt .-%, based on the total mass of the supported catalyst.
  • the catalytically active components are expediently brought to the support in the form of a solution, then the solvent is evaporated off and the catalyst is dried. Water, hydrochloric acid, nitric acid, alkali solutions or aqueous ammonia solution, preferably water and hydrochloric acid, are generally used as solvents.
  • the active components can also be used without a carrier.
  • the oxidative dehydrogenation is preferably carried out generally at temperatures between 100 and 600 ° C, between 200 and 400 0 C.
  • the residence time is preferably between 0.1 and 10 seconds, but in particular between 0.1 and 1 second. Satisfactory results are still obtained even outside these limits.
  • Oxydehydrogenation is preferably carried out at normal pressure, but reduced or increased pressures can also be used, i.e. 0.01 to 100 bar.
  • the procedure is such that the glycolic acid ester and oxygen or oxygen-containing gas, and optionally the carrier gas, are fed from metering devices into an evaporation zone and the resulting gas mixture is then passed through a reaction tube which is heated from the outside and filled with the catalyst. It has proven advantageous to heat the oxygen or the oxygen-containing gas and the carrier gas to the reaction temperature before they are introduced into the evaporation zone.
  • the gaseous reaction mixture is quenched (quenched) with an entrainer immediately after leaving the reactor and passed directly into the middle part of a fractionation column.
  • the top product of the column contains the water and the alcohol formed as a by-product, as well as small amounts of other by-products such as formaldehyde and formic acid ester.
  • the sump consists essentially of the glyoxylic acid ester and possibly unreacted glycolic acid ester; the glyoxylic acid ester can be separated from this mixture by conventional distillation.
  • the entrainer can then be extracted from the top product by known methods, e.g. obtained by distillation or by phase separation and recycled.
  • entrainer all substances which form azeotropes with water and alcohols are suitable as entrainer.
  • a water-immiscible entrainer is preferred because this can then be separated off and returned as a separate phase after the condensation of the top product.
  • the boiling point of the entrainer is preferably below the boiling point of the particular glyoxylic acid ester. However, at least the boiling point of the azeotrope must be below the boiling point of the glyoxylic acid ester.
  • Suitable entraining agents are aliphatic and aromatic hydrocarbons, which may contain heteroatoms, such as CH 2 Cl 2 , CHCl 3 , CC14, n-pentane, n-hexane, cyclohexane, nonane, diisopropyl ether, methyl ethyl ketone, benzene and toluene, especially n-pentane and Cyclohexane.
  • glyoxylic acid esters are valuable starting and intermediate products for a number of syntheses of pharmaceutically active compounds, e.g. Allantoin, substituted glycine or alkaloids (such as tetrahydroisoquinoline alkaloids).
  • An aluminum silicate with a BET surface area of 1 m 2 g -1 is used as a support for the catalyst.
  • the catalyst contains 7.8% by weight of Ag and 3.7% by weight of V.
  • 2.0 g of vanadium pentoxide is dissolved in 15 ml of concentrated hydrochloric acid, 30 g of catalyst support are soaked in this solution and the solvent is evaporated the steam bath.
  • 3.7 g of silver nitrate are applied after dissolving in 6 ml of water.
  • the catalyst is then dried at 110 ° C.
  • 7.5 ml of this catalyst are in a vertically arranged glass reactor 150 mm long and 20 mm in diameter was filled and heated in a gas stream of 45 mmol / h oxygen and 2.5 mol / h nitrogen at 400 ° C. for three hours.
  • the reactor is heated from the outside and the temperature inside is measured using a thermocouple.
  • test After a start-up time of 1 hour to set constant operating conditions, the test is continued over a period of 4 hours.
  • the gaseous reaction products are quenched with 150 ml / h of n-pentane as entrainer and passed into the middle section of a fractionation column (length: 600 mm, diameter: 55 mm, filling: Braunschweig Wendeln).
  • the column temperature is 70 ° C in the upper part and 90 ° C in the lower part.
  • a 2-phase condensate is obtained at the top of the column.
  • 5.6 g of aqueous phase are produced with the composition:
  • the bottom product consists predominantly of methyl glyoxylate (17.0 g), corresponding to a yield of 74.5%, based on the glycolic acid methyl ester used.
  • Example 2 Analogously to Example 1, 6 ml / h of n-butyl glycolate (46.3 mmol / h), 44.6 mmol / h of oxygen and 2.5 mol / h of nitrogen are introduced into the apparatus described there.
  • the reactor is filled with 15 ml of a supported aluminum silicate catalyst which contains 8.05% by weight of Bi and 1.95% by weight of V on a support as in Example 1.
  • the reaction temperature is 250 ° C.
  • reaction products are quenched with 20 ml / h of cyclohexane as entrainer and passed into the middle part of the column.
  • the column temperature is 95 ° C in the upper part and 100 ° C in the lower part.
  • a 2-phase condensate is obtained at the top of the column.
  • the bottom product contains 10.3 g of n-butyl glyoxylate, corresponding to a yield of 42.1%, based on the n-butyl glycolate used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84107326A 1983-06-29 1984-06-26 Procédé de préparation d'un ester de l'acide glyoxylique Expired EP0130533B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84107326T ATE18759T1 (de) 1983-06-29 1984-06-26 Verfahren zur herstellung eines glyoxylsaeureesters.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3323372 1983-06-29
DE3323372A DE3323372A1 (de) 1983-06-29 1983-06-29 Verfahren zur herstellung eines glyoxylsaeureesters

Publications (2)

Publication Number Publication Date
EP0130533A1 true EP0130533A1 (fr) 1985-01-09
EP0130533B1 EP0130533B1 (fr) 1986-03-26

Family

ID=6202655

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107326A Expired EP0130533B1 (fr) 1983-06-29 1984-06-26 Procédé de préparation d'un ester de l'acide glyoxylique

Country Status (7)

Country Link
EP (1) EP0130533B1 (fr)
JP (1) JPS6023345A (fr)
AT (1) ATE18759T1 (fr)
AU (1) AU560545B2 (fr)
CA (1) CA1224216A (fr)
DE (2) DE3323372A1 (fr)
ZA (1) ZA844935B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2588866A1 (fr) * 1985-10-23 1987-04-24 Hoechst France Procede de fabrication de glyoxylate d'alkyle
US4820385A (en) * 1988-02-18 1989-04-11 Monsanto Company Purification of alkyl glyoxylate in a continuous column by azeotropic distillation
US4867849A (en) * 1988-07-25 1989-09-19 Cova Dario R Purification of alkyl glyoxylate
US4900864A (en) * 1988-08-09 1990-02-13 Anantaneni Prakasa R Manufacture of alkyl glyoxylates with ferric phosphate catalyst
EP0673914A2 (fr) * 1994-03-25 1995-09-27 Ube Industries, Ltd. Préparation d'esters d'alpha-céto-acides
CN112354542A (zh) * 2020-11-20 2021-02-12 浙江工业大学 一种V2O5-CuO/TiO2催化剂及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5217582A (en) * 1990-06-20 1993-06-08 E. I. Du Pont De Nemours And Company Process for the isolation of alkyl glyoxylate
JP3150909B2 (ja) * 1996-09-05 2001-03-26 株式会社日本触媒 グリオキシル酸エステル類の精製方法
JP2013027475A (ja) 2011-07-27 2013-02-07 Brother Ind Ltd 多針ミシン

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE447838C (de) * 1923-03-06 1927-08-08 Boehringer Sohn Ingelheim Verfahren zur Herstellung von Oxosaeureestern und Oxosaeuren
DE2904775A1 (de) * 1979-02-08 1980-08-28 Hoechst Ag Verfahren zur herstellung von glyoxylsaeureestern

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE447838C (de) * 1923-03-06 1927-08-08 Boehringer Sohn Ingelheim Verfahren zur Herstellung von Oxosaeureestern und Oxosaeuren
DE2904775A1 (de) * 1979-02-08 1980-08-28 Hoechst Ag Verfahren zur herstellung von glyoxylsaeureestern

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0225223A1 (fr) * 1985-10-23 1987-06-10 SOCIETE FRANCAISE HOECHST Société anonyme dite: Procédé de fabrication de glyoxylate d'alkyle
FR2588866A1 (fr) * 1985-10-23 1987-04-24 Hoechst France Procede de fabrication de glyoxylate d'alkyle
US4820385A (en) * 1988-02-18 1989-04-11 Monsanto Company Purification of alkyl glyoxylate in a continuous column by azeotropic distillation
EP0329637A2 (fr) * 1988-02-18 1989-08-23 Monsanto Company Epuration de glyoxylate d'alkyle en colonne continue par distillation azéotropique
EP0329637A3 (en) * 1988-02-18 1990-08-01 Monsanto Company Purification of alkyl glyoxylate in a continuous column by azeotropic distillation
EP0353215A3 (en) * 1988-07-25 1990-08-08 Monsanto Company Purification of alkyl glyoxylate
US4867849A (en) * 1988-07-25 1989-09-19 Cova Dario R Purification of alkyl glyoxylate
EP0353215A2 (fr) * 1988-07-25 1990-01-31 Monsanto Company Purification d'alkylglyoxylate
US4900864A (en) * 1988-08-09 1990-02-13 Anantaneni Prakasa R Manufacture of alkyl glyoxylates with ferric phosphate catalyst
EP0673914A2 (fr) * 1994-03-25 1995-09-27 Ube Industries, Ltd. Préparation d'esters d'alpha-céto-acides
EP0673914A3 (fr) * 1994-03-25 1995-11-22 Ube Industries Préparation d'esters d'alpha-céto-acides.
CN112354542A (zh) * 2020-11-20 2021-02-12 浙江工业大学 一种V2O5-CuO/TiO2催化剂及其制备方法和应用
CN112354542B (zh) * 2020-11-20 2023-07-11 浙江工业大学 一种V2O5-CuO/TiO2催化剂及其制备方法和应用

Also Published As

Publication number Publication date
DE3460060D1 (en) 1986-04-30
DE3323372A1 (de) 1985-01-10
ATE18759T1 (de) 1986-04-15
ZA844935B (en) 1985-02-27
CA1224216A (fr) 1987-07-14
EP0130533B1 (fr) 1986-03-26
AU3000784A (en) 1985-01-03
AU560545B2 (en) 1987-04-09
JPS6023345A (ja) 1985-02-05

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